Thiazoles



Patented Sept. 19, 1944 THIAZOLES Paul C. Jones and Arthur W. Sloan, Akron, Ohio, assignors to The B. F. Goodrich Company, New York, N..Y., a corporation of New York No-Drawing; Original application April 5, 1939, Serial-No. 266,130; Divided and this application September 22, 1942, Serial No. 459,294

8 Claims. (01: 260-j302).

This invention has as its object the preparation of a new class of compounds useful as vulcanization accelerators.

We have discovered that bis-mercaptomethyl amines having the general formula wherein R represents an organic radical with the free valence on a carbon atom, A represents an' alkylene group, Y represents a'hydrocarbonradh cal with a valence not greater than two and n is equal to the'valence of Y, are easily prepared and are excellent accelerators of vulcanization.

These compounds fallinto two genera-lclasses,

namely, the bis-mercaptomethyl amines derived from amines containing one primary amino. group such as ethylamine or aniline, and the blS"-mEl"-' captomethyl amines derived from polyamines such as ethylene diamine or p-phenylenediamine. The preferred compounds derived from monoamines have the general formula (R--SCH2-) 2NY wherein R representsan organic radical with the free valence on a carbon atom and Y represents a monovalent hydrocarbon group.

These compounds may be considered as being derived from sulfhydryl (Rf-SH) compounds, and may be conveniently grouped according to the sulfhydryls to which they are related.

When the compoundsare derived from 'mer captans, R. represents methyl,- ethyl, isopropy'l,

allyl; cyclohexyl, benzyl, phenyl, ortho, meta,- or para tolyl, naphthyl, anthryl, in'danyl, chlor phenyl, methoxyethyl, anisyl, anilinophenyl, furyl, etc; Such specific compounds as bis-phenylmercaptomethylethylamine, bis-betanaphthylmercaptomethyl ethyl amine, and related compounds fall within this class.

' Other members ofthis new class of compounds" may be considered as derived from carbothiolic and carbodithioic acids, in which case R'repre sents such groups as. methanecarbothionyl,.eth-

anecarbothionyl, benzenecarbothionyl, 3-furanecarbothionyl, acetyl', ,3-furoyl, andrelated-groups.

Such. specific compounds as bis benzenecarbothionylmercaptomethyl ethyl amine and bis-acetylmercaptomethyl ethyl amine are typical compounds of this type.

R may also be derived from a dithiocarbamic acid and represent such groupsas dimethylthiocarbamyl, methyl ethyl thiocarbamyl, ethyl-thiecarbamyl," methyl-p'henyl-thiocarbamyl, ethylbe 11 'zy l thiocarbamyl, diphenylthiocarbamyl,

phenyl-alpha-naphthyl-thiocarbamyl, phenylpara-chlorphenyl-thiocarbamyl, o,o'-dimethylmethylenediphenylthiocarbamyl,v phenyl-paraisopropylphenyl-thiocarbamyl,

phenyl-para-hydroxyphenyl-thiocarbamyl, p h e n y-lanilinophenyl-thiocarbamyl and similar groups. The diaryldithiocarbamic derivatives, of which bis diphenylthiocarbamylmercaptomethyl' ethyl.

amine; is typical member, are preferred.

Other members of this'n'ew class of compounds may .be considered asderived from azoles, azines, and azolines. In this case, B represents such groups as Z-thiazyl 2r-benzoithiazyl, Z-naphthothiazyh. 2-benzooxaz'yl, 2-benzoimidazyl, 4,5-dithiazolinyl', 4,5-dimethyl-2 thiazolinyl,' and similaroxazine and thiazine derivatives. Preferred compounds inthis'class' include bis-2-thiazolinyhnercaptomethyl ethyl amine,

bis-=2-benzothiazylmercaptomethyl ethyl amine;

2-benzothiazylmercaptomethyl 2-thiazolinylmercapt'omethyl ethyl amine; bis-2-'(4',5'-dimethylthiazyl) inercapt'omethyl ethyl amine. and like derivatives of other thiazolin'es and alkyl and arylene thiazoles.

It is to be understood Y is not restricted to ethyl, but may be methyl, isopropyl, vinyl, cyclohexyl, benzyl, phenyl, Xenyl, naphthyl, and. other, univalent hydrocarbon groups. Although the hismercaptomethylamines are preferred, bis-mercaptoethyl amines or compounds in which A represents other alkylene groups are within the broad scope of the invention.

The second class of compounds, formed where &3! divalent, are derived from diamines. The

preferredcompounds have the generalformula I (ms-0H?)2N v;1v cHa-s -R 2.

wherein R represents an organic radical with a free valence on a carbon atom and Y represents a divalent hydrocarbon group. It may represent rubber 100 parts, zinc oxide 'parts, sulfur 3 the wide variety of radicals heretofore described, parts, and stearic acid 1 part, the composition and Y may represent ethylene, propylene, phenattained a tensile strength of 2395 lbs/in. when ylene, naphthylene, xenylene, cyclohexylene, and heated in a press for 60 min. at 220 F., and a similar alkylene and arylene groups. Typical ac- 5 tensile strength of 3410 lbs. /in. when heated for ,celerators within this class comprise min. at 287 F.

N,N,N',N'-tetrakis-diphenylthiocarbamylmercap- 1 Example 11 tomethyl-ethylenediamine, 15 5 benzot'hiaz ylmercaptomethyl cyclohexyl JL ,N benzothlazylmercapto amine was prepared by the following stoichiomethyl ethylenediamme, Y metric reaction.

N,N,N',N-tetrakis-2- (4,5-dimethy1thiazyl) mercaptomethyl ethylenediamine,

' C-SH+2CHzO'l-CaHnNH2 N,N,N',N tetrakis-2-thiazolinylmercaptomethyl ethylenediamine, etc a r r 2 The compounds of this invention may in'general be prepared by reacting, in proper propor- S N tions, a metallic salt of a sulfhydryl compound with an aldehyde and a primary amine salt in ac- H +211 0 cordance with the following equation: ,7 2 2RSNa+2CHz-l-2YNH2-HClp n s a 2 (R,SCI-I2 )2NY-+ +2NaCl-l2 The materials were dissolved in a small volume These reagents interact when brought into conof acetone, and a precipitate ua y forme tact, even at room temperature, although they and was isolated by evaporating the acetone and may be warmed somewhat if desired; and are Waterr preferably reacted in a liquid medium such as A composition Containing rubber 100 p s y water, alcohol, acetone, benzene or the like. Weight, Sulfur P Zinc Oxide 5 p lallric Certain sulfhydryl -compounds such as the 5 acid 3 p a t e above accelerator 1 part, thiazoles and thiazolines undergo an'addition redeveloped a tensile r h of 7 l -fi action with formaldehyde to form thioallqyl- W en cured in a heated mold for 15 min. at enehydrins which are useful reactantsfor the 1 v I preparation of the compounds of this invention Example III in accordance W1th t e fo i equatlon? 4o Bis-2-thiazolinylmercaptomethyl cyclohexyl 2R 3 a amine was prepared by the following stoichio- (R.'SCHz)zN-Y+2H2O metric reaction: Detailed instructions for carrying out reac- HzN tions of these types are disclosed in the prior 2 I H, CGHHNH,

patents of Coleman No. 1,901,582 and Bunbury 5- H S et al. No. 1,972,918. Other methods of prepara- 7 tion which will be apparent to those skilled in z-N the art may be employed, the preferred method being ordinarily determined by the sulfhydryl H S compound to be employed. f I P 2 In order to more clearly illustrate our inven- The s 'fi O c rs n Simple mixing of the tion, and the preferred modes, OLCarrying t materials, with considerable evolution of heat, same into effect, the following examples are and may be completed by further heating, Which given; also removes water from the product.

Example, I wei ht, sulfur 3.5 a ts, zin BS'mphenymmmarbamylmemaptomethyl eththe above accelera toi 1 part 11 25551 12; Z 31 Y1 amine was prepared by the reamion repre' lowing characteristics when vulcanized in a 55 A composition containing rubber'100 parts by sented stoiehiometrically as follows: heated mold. H

2C2H5NH2.HC1+2 N -C. S Na+2CH 0 Time of cure in min. at 287 F. ggi g Elongation a 15 4 3,770 5 30 3, 570 V V 760 i NC2H5+ When 3 parts of lauric acid wereincluded in the O 2 p above recipe, the following results were obtained:

1 V zfimwonimE-l-mo 1 Tensil I 2 r. The ingredients were dissolved in water and ,uneo cmemmm at 87 Strength Elongatwn mixed, whereupon a white precipitate formed, M I which was filtered off and'dried. 15 l V V Lbs-411 Pcr cengso When 0.5 part by weight of this acceleratorv 7' 7 .1 1 41250 710 was incorporated in a composition containing This invention is not limited to the specific examples herein set forth, for it will be obvious wherein R represents an organic radical with the free valence on a carbon atom, Y represents a. hydrocarbon radical with a valence not greater than two and n is equal to the valence of Y.

2. A compound having the formula wherein R represents an organic radical with the free valence on a carbon atom and Y represents a monovalent hydrocarbon radical.

3. A compound having the formula (RSCH2) 2N Y wherein R represents a 2-thiazyl radical and Y represents a saturated monovalent hydrocarbon radical.

4. Bis-Z-benzothiazylmercaptomethyl hexyl amine.

5-. A compound having the formula wherein R represents a 2-thiazolinyl radical and Y represents a saturated monovalent hydrocarbon radical.

6. Bis-2-thiazolinylmercaptomethyl cyclohexyl amine.

7. A compound having the formula wherein R represents an organic radical with the free valence on a, carbon atom and Y represents a divalent hydrocarbon radical.

8. N,N,N',N'- tetrakis 2 thiazolinylmercaptomethyl ethylene diamine.

PAUL C. JONES. ARTHUR W. SLOAN.

cyclo- 

